DE2807787A1 - UREA COMPOUND WITH A CARBOXYLATE RESIDUE AND THE PROCESS FOR THEIR PRODUCTION - Google Patents

Description

The invention relates to a new electrolyte compound and a method of making them; in particular, it relates to a new urea compound with a carboxylate residue and a process for their preparation (the "urea compound having a carboxylate residue" described herein can also be called "Carboxylate urea compound" or "carboxylate polyurea" are designated).

Many synthetic high molecular weight substances have the disadvantage that they have poor moisture absorption properties, have poor antistatic properties and dyeability and the like, so that usually Additives such as plasticizers or surface-active agents to improve their properties in this regard must be used. However, these types of improvement are accompanied by various disadvantages such as: B. those that the additive is reduced with the lapse of time, that phase separation occurs, and the like. It is therefore most preferably to polymerize or copolymerize moisture or water absorbing monomers independently. However, when carrying out the polyaddition or the polycondensation, full attention should be paid should be directed to the selection of the appropriate starting materials and the polymerization process used, because the presence of a moisture or water absorbing functional group in some kinds of the starting materials to an inhibition (inhibition) or prevention of the polymerization under the influence of the polarity of the functional Groups can lead or these can be consumed and cleaved ornaments during the polymerization reaction.

The aim of the present invention is therefore to provide a new

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Carboxylate urea compound indicate which has many advantages over the conventional substances with a high molecular weight with respect to various properties, such as e.g. B. the water solubility, its hydrophilic properties, their water absorption properties and their antistatic properties. The aim of the invention is also a method for producing such a carboxylate urea compound to specify.

The urea compound according to the invention with a carboxylate residue can generally be represented by the general formula

OX X ¹ O OX X ¹ OXX ¹ O

I - +
R-COO MR ₅

where mean:

R _{1 is} a divalent hydrocarbon radical with 2 to 17 carbon atoms or a divalent polymer radical with an average molecular weight of 10,000 or less,
Ri Riii

R ₂ denotes the -C- Cf ^ radical, wherein Ri, Rii, Riii and Riv, respectively

Rii Riv

independently of each other a hydrogen atom, a monovalent one Hydrocarbon radical with 1 to 10 carbon atoms or another monovalent radical that is associated with isocyanato or amino residues not reacting, represent,

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where at least one of the radicals Ri "and Rii is hydrogen atom means

R, a divalent hydrocarbon radical with 4 to 25 Carbon atoms or a polyether or polyester radical with an average molecular weight of 10,000 or less,

R ^ is a divalent hydrocarbon radical with 2 to 17 Carbon atoms,

Rc and R _6, independently of one another, each represent a hydrogen atom or a monovalent hydrocarbon radical with 1 to 8 carbon atoms, or Rc and Rg represent divalent hydrocarbon radicals which, through mutual bonding, together form a carbon chain with 2 to 13 carbon atoms or their side chain substituents,

X and X ¹ independently of one another each represent a hydrogen atom or -GONH radicals,

M ⁺ a cation and

x, y and ζ values which indicate the relative molar proportions of the respective corresponding units and which meet the required conditions: x + y + z = 1 and 0.1 ^ 100x / (x + y + z) ^ 100. The α-carbon atom in the radical R2 is directly connected to the carbon atom of the carboxylate radical -COO ~ M ⁺ .

The carboxylate urea compounds of the general ones given above Formulas can be of the following four types

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to be grouped:

(1) Those in which χ = 1, j = O and ζ = 0, ie in which only the component χ is present

OX X ¹ O

R ₂ -COO ~ M ⁺

(2) Those in which ζ = O, ie in which the. Components χ and j are present

OX X ¹ O OX X ¹ O

Ί l

sicNR_N-c> Tr — tNR ^ NCNR ^ N-c-hr- (Formula B)

_ + I I

R ^ -COO M ⁺ R ₅

where x + y = 1 and 0.1 ^ 100x / (x + y) <: 100.

(3) Those in which y «O ₁ d. h · the components χ and ζ are present

ox X ¹ O x x'o

R ₂ -COO M ⁺

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where x + a = 1 and O _i i <100x / (x + z) <100 < ₎

(4 ·) Those in which the components x, y Tand ζ are all present are

OX X ¹ O OX X ¹ OXX ¹ O

3 ^; z (formula D)

R ₂ -COO M ⁺ R ₅ R

where x + y + z = 1 and 0.1 ^ 100x / (x + y + z) <. 100 _e

It should be noted that each of the general Formulas A through D merely indicate the components, compositions or structures of each unit, that these However, it is not intended to define the configuration or direction of each unit.

While Σ and X ¹ mean hydrogen atoms or -CONH radicals, which represent amide bonds, the molar amount of the -COKH radical should preferably be 30 % or less of the total molar amounts of X and X ', because too many biuret bonds compared to the hydrogen bonds are too intermolecular Can lead to cross-links, which result in gelation and the like, as a result of which the usefulness of the product is reduced, for example in that the resulting polymer tends to become thermosetting.

Under the term "hydrocarbon residue" used here are generally the hydrocarbon residues (aliphatic, alicyclic, aliphatic-substituted alicyclic,

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aromatic, aliphatic-substituted aromatic, alicyclic-substituted aromatic and aliphatic-substituted alicyclic-substituted aromatic radicals) and substituted hydrocarbon radicals replaced by non-hydrocarbon radicals (such as halogen, cyano group and the like) are substituted with the other starting materials not reacting and not inhibiting or delaying the desired reaction, understanding.

In the formulas given above, R ^ means a divalent one Remainder obtained by eliminating the two amino groups from primary diamines known per se. To such Diamines include aliphatic diamines with 2 to 17 carbon atoms, such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, heptadecamethylenediamine, 1,2-diaminopropane, 2,2,4-trimethylhexamethylenediamine, and the like; alicyclic or aliphatic-substituted alicyclic diamines with 6 to 15 carbon atoms, such as 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-diamino-i-methylcyclohexane, 3 »5-diamino-1,1-dimethylcyclohexane, 1,5-diamino-1,3-dimethylcyclohexane, 3j1-diamino-i-methoxyethylcyclopentane, i ^ -Diamino-i-methyl ^ -niöthoäthylcyclohexan, 1,4 -Di-

1 2 amino-i-methyl - ^ - methoäthylcyclohexane, 1, 3 -diamino-1-

methyl-3-dimethoethylcyclopentane, ^, ^ '- diaminodicyclohexyl methane and the like; aromatic or aliphatic-substituted aromatic diamines, such as m-phenylenediamine, p-phenylenediamine, ^ -ethylphenylenediamine- (1,3), 2-methylphenylenediamine- (1,3), 3-aminobenzylamine, 4-aminobenzylamine, 4-amino-y6 -phenethylamine, p-2ylylenediamine, 4,4'-diaminodiphenylmethane, 3 »3'-dichloro-4,4 ¹ -diaminodiphenylmethane. In addition, R ^ can contain any functional group (s) associated with the amine or isocyanato radicals

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neither react nor retard or inhibit their polymerization reaction. Examples of diamines which contain this radical R ^ are halogen-substituted aromatic diamines, ω , co '-diaminopolyethers and ω , ω * -diaminopolyesters, the last-mentioned two polymer diamines having a repeating unit of 2 to 20 carbon atoms and an average molecular weight of 10,000 or less, preferably of 104 or more.

R2 denotes an ethylene radical and an ethylene-based radical in which the ethylene radical is substituted by one or more hydrocarbon radicals or one or more functional radicals, e.g. B. Formamido-j acetamido, phthalimide, methoxy, ithoxy, halogen and similar radicals that do not react with the isocyanato or amino radical. Examples of R ₂ are the ethylene radical, oil-substituted ethylene radicals, such as ct-methylethyleneT, Oi.-Ethyläthylen-, QL-Phenyläthylen-, Ot -Formamidoäthylen-, oi-Acetamidoäthylen-, Ol-Phthalimidoäthylen-, QC - Methoxyethylene, Qd. -Äthoxyäthylen-, OL -Chloräthylen-, oL-bromoethylene-, oil -Cyanoäthylen-, CL-Acetoxyäthyien- and similar residues; Ot, oL-disubstituted ethylene radicals, such as oi, OL-dimethylethylene, Ot, qL_Bis- (chloromethyl) -ethylene, d, csL-diacylamidoethylene and similar radicals; CL, β- disubstituted ethylene radicals, such as oil, β -dichlorethylene, Qi-methyl-y3 -chlorethylene, οι -Cyano- β -phenylethylene and similar radicals; and β- substituted ethylene radicals, such as β- methylethylene, / 3-phenylethylene, / 3-ethoxyethylene, β -chlorethylene and similar radicals.

R, stands for a divalent radical that is eliminated by elimination of the two isocyanate radicals of diisocyanates is obtained, as is commonly known as a starting material for

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Polyurethanes or polyureas are used and represent the starting material according to the invention. Such diisocyanates include aliphatic diisocyanates having 4 "to 16 carbon atoms, such as butane-1,4-diisocyanate, hexane-1,6-diisocyanate, nonane-1,9-diisocyanate, 2-methylbutane-1,4-diisocyanate, dimethylsilane diisocyanate and the like; alicyclic diisocyanates having 8 to 20 carbon atoms, such as cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1-ethylcyclohexane-2,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, U) , ω '-1, ^ - dimethylcyclohexane diisocyanate and the like; aliphatic-substituted aromatic diisocyanates having 9 to 20 carbon atoms, such as ^ -phenyl isocyanate methyl isocyanate, 4-phenyl isocyanate-y? -ethyl isocyanate and the like; alicyclically substituted aromatic diisocyanates having 12 to 20 carbon atoms, such as Tetrahydronaphthylene-i ^ -diisocyanate, hexahydrodiphenylmethane-4,4'-diisocyanate and the like; as well as aromatic diisocyanates with 8 to 25 carbon atoms, such as 1,3-phenylene diisocyanate, 1,4-phenylene _{diisocyanate, H} 1-methylbenzene-2,4-diisocyanate, 1-Me ethylbenzene-2,6-diisocyanate, naphthalene-2,7-diisocyanate, diphenylmethane-4,4'-diisocyanate and the like. They also include polyesters and isocyanate-terminated polyethers which have an average molecular weight of 10,000 or less, preferably 302 or more, which can be prepared by a known method.

R ^, Rc and Bg represent the best that can be obtained by eliminating the amino esters from the diamines of the formula

HN E ₄ NH

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Such diamines include aliphatic secondary and primary secondary diamines with 3 to 28 carbon atoms, such as H-methylethylenediamine, N-ethylethylenediamine, N-propylethylenediamine, N-methyltetramethylenediamine, N- (<j -chlorobutyl) pentamethylenediamine, H-methyl! hexamethylene diamine, H-Äthylhexamethylendiamin _s N-Propylhexamethylendiamin, N-Isobuty! hexamethylenediamine, H, N '~ dimethylethylenediamine, J ^ IT' D äthyläthylendiamin, UjN'-Dimethyltetramethylendiamin, Η, Η ¹ -Dimethylhexamethylendiamin! ■ 'M' Diäthylhexamethylendiamin , 1,10-bis-octylamino-2 _t 9 ™ dimethyldecane and the like; ali »cyclic secondary and primary-secondary diamines with 5-26 carbon atoms, such as N-methyl-1, ^ - diaminocyclohexane, N ^ '- dimethyl-ijÄ-diaminomethylcyclohexane, piperazine, azacycloheptane, 1,15-diazacyclooctacosane and the like; aromatic secondary and primary-secondary diamines with 7-21 carbon atoms, such as H-methyl-m-phenylenediamine, N, H'-dimethyl-m-phenylenediamine, N-ethyl-m-phenylenediamine, Ui ₉ K ¹ ^ diethyl-m- phenylenediamine, K-methyl-p-phenylenediamine, N, 3S'-dimethyl-p-phenylenediamine, IT-ethyl-p-phenylenediamine, BT-propyl-p-phenylenediamine, JST, N ¹ -dimethyl-4-methy! phenylenediamine »(1 , 3) K ₁ H '~ Diniethyi-2-methylphenylenediamine »(1,3), N, N ¹ -dimethyl-4,4'-diaminediphenylmethane and the like, as well as the diamines mentioned above in relation to the radical E / j They also include polyamines in which the total number of primary and secondary amino groups is 2 and in which the other amino groups are tertiary amino groups, such as, for example, in 1- (2'-amino ethyl) piperazine _s 1,4-di- (2'-aminoethyl) piperazine and the like.

Examples of M are alkali metals such as lithium, sodium, Potassium and the like; Alkaline earth metals such as magnesium, calcium, strontium, barium and the like; as well as tertiary

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Amines such as trimethylamine, dimethylethylamine, triethylamine, dimethylpropylamine, dimethylisopropylamine, methylethylpropylamine, methyldipropylamine, methylpropylbutylamine, pyridine, N-methylmorpholine, Ν, Ν-dimethylaniline, triethylenediamine and the like. However, M is by no means restricted to the examples given above. In general, M is a basic substance which can form a carboxylate salt and whose corresponding cation M ⁺ does not react with an isocyanate.

X and X ¹ have already been discussed in more detail above.

The carboxylate urea compound of the present invention can be produced are made by reacting an aminoaminocarboxylate of the general formula

, -COO ^- M ⁺ (I)

with a diisocyanate of the general formula

OCNR ^ NGO (II)

optionally in the presence of a diamine of the formula

HN R ^ NH

R ₅ R ₆ (III)

and / or water. When an aminoaminocarboxylate (I) and a diisocyanate (II) are allowed to react with each other alone, is obtained one compound of formula A. If such a

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Reaction is accompanied by the addition of a diamine (III) or from water, then one obtains a compound of the formula B or C. Of course, if the reaction is carried out with the addition

both a diamine and water is carried out, a compound of formula D is obtained.

Aminoaminocarboxylic acids or salts thereof (I), one of the starting materials of the process according to the invention, can be prepared by reacting, for example, β- propiolactone with a diamine, as described in "Kogyo ~ kagaku Zasshi" 73 , 1720 (1970) by S. Katayama, S Horikawa and M. Ohbucchi stated.

R ^ and R2 have already been discussed above. Examples of aminoaminocarboxylic acids are aliphatic aminoaminocarboxylic acids having 5 to 21 carbon atoms, such as. B. N- (2-carboxyethyl ethylenediamine, N- (2-carboxyethyl) trimethylenediamine, N- (2-carboxyethyl) hexamethylenediamine, N- (2 ~ methyl-2-carboxyethylhexamethylenediamine and the like; aliphatic-substituted alicyclic aminoaminocarboxylic acids with 9 to 19 Carbon atoms, such as N- (2-carboxyethyl) -1, 4-diaminocyclohexane, 3-N- (2-carboxyethyl) -1,3-diamino-i-methylcyclohexane, N- (2-carboxyethyl) -4.4 * - diaminodicyclohexylmethane and the like; as well as aliphatic-substituted aromatic aminoaminocarboxylic acids with 9 to 19 carbon atoms, such as N- (2-carboxyethyl) -pphenylenediamine, N- (2-carboxyethyl) -p-xylylenediamine, N- (2-methyl-2-carboxyethyl) -p-xylylenediamine, N- (2-oxyethyl) -4,4'-diaminodiphenylmethane, N, N ¹ -di (2-carboxyethyl) -3,3 · dichloro-4,4'-diaminodiphenylmethane and the like.

These aminoaminocarboxylic acids can be in the form of aminoamino-

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carboxylates are used with a prescribed Base M neutralized and prior to making the carboxylate urea compound have been isolated, or the aminoaminocarboxylic acid can by another method with the Base H can be neutralized and used for the polymerization without isolation, using the urea compound receives.

Typical examples of diisocyanates (II) and diamine (III) are already given above.

The carboxylate urea compound of the present invention can be produced are made by interface polymerization, by solution polymerization and by solvent-free polymerization, as explained in more detail below. The aminoaminocarboxylate, the diamine and the water can, if desired, beforehand are mixed with each other before the polymerization reaction is carried out because they do not react with each other in either case.

When one or more primary or secondary amino radicals are reacted with one or more isocyanato radicals, polymerization catalysts are not absolutely necessary, since the reaction generally proceeds at a considerable rate. However, when accelerating the rate of polymerization or when using weakly basic aromatic diamines, catalysts should preferably be used. These catalysts are known per se and are those used for the production of polyurethanes and polyureas, and they include tertiary amines such as triethylamine, N-methylmorpholine, N, N, N ¹ ,! T-tetramethylpropyl -

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diamine, N, N, N ¹ , N'-tetramethyl-1, 3-butanediamine ₉ Ν, Ν, Ν ¹ , N ¹ -tetramethyl! hexamethylenediamine, Ν, Ν-dimethylbenzylamine, N, N-methyllaurylamine, NjN'-dimethylpiperazine , Triethylenediamine ■ and the like; Tin compounds such as tributyl tin acetate, dibutyl _{tin diacetate, dibutyl tin dilaurate, dibutyl tin sulfide, dibutyl tin dichloride, tin (IY) chloride 9} tin (II) octoate, tin (II) oleate and the like; Lead compounds such as lead benzoate, lead oleate and the like; Cobalt 2-ethylhexoate, cobalt naphthenate _{s s} cobalt benzoate, and the like cobalt compounds such as; Zinc compounds such as zinc naphthenate, zinc ~ 2-ethylhexo-fe and the like; Carboxylic acids such as η-butyric acid, valeric acid and the like; and ureas, such as N-phenyl-U'-o-toly! urea «However, those which react with amines to form substances which can destroy the carboxylate structure or inactivate their own catalytic effects, such as e.g. B. chlorocarboxylic acid, hydrochloric acid, sulfuric acid and the like can selectively accelerate the reaction between the xocyanate radical and the water. These catalysts include, for. B. Tin (II) ocbate and N-ethylmorpholine. On the other hand, dibutyltin diacetate, tributyltin acetate, triethylenediamine and the like accelerate the reaction with water to increase component z, and dibutyltin dilaurate is also an intermediate between these two types.

Although the carboxylate urea compounds of the invention have already been described above, belong to it

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also those with a branched or networked structure, which is a consequence of the formation of partial biuret bonds by the reaction of the IT-hydrogen residue of the urea bond with the isocyanato-Hest, whereby the production of a such branched or crosslinked structure through catalysts such as dibutyltin diacetate, tributyltin acetate and triethylenediamine, which accelerate the urea isocyanato reaction, can be facilitated. If such a branched or crosslinked structure is not desired, will accordingly these catalysts are not used. To the catalysts that favor the formation of biuret bonds (Accelerate) include tin compounds, such as dibutyltin diacetate and QJributyltin acetate, triethylenediamine, the above Zinc compounds and the like.

Many of the aminoaminocarboxylates represented by Formula I. and their corresponding aminoaminocarboxylic acids generally have high melting points and they dissolve in highly polar protic solvents such as water and lower hydrocarbon alcohols as well as in highly polar solvents with high dielectric constants, such as H, N-dimethylformamide and dimethyl sulfoxide, being in others weakly polar solvents are hardly soluble. An aminoaminocarboxylic acid with a lower ion density, i.e. H. with a higher molecular weight but has a lower one Melting point and better solubility. Therefore, the polymerization method and conditions should can be selected depending on the melting point and solubility of the aminoaminocarboxylic acid or its salt (I). When using protic solvents such as water and the like, the polymerization can be carried out, when the reactivity of the aminoaminocarboxylate (I)

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is sufficiently higher than that of the protic solvents or, if one of the catalysts is used, the "Preferably accelerate the reaction with amino groups, as stated above. The polymerization can also be carried out are when using the so-called interfacial polymerization process, in which a misoeyanate (II) in a non-polar solvent that with the protic solvents is immiscible, is dissolved in which an aminoaminocarboxylate (I) is dissolved in a protic solvent and the two solutions thus obtained are mixed together and then polymerized at the interface takes place.

Most commonly used are polar aprotic solvents, such as dimethylformamide and dimethyl sulfoxide. A solution the aminoaminocarboxylate (I) for polymerization with diisocyanate (II) can be prepared by dissolving the Aminoaminocarboxylic acid and a base M in these solvents or by another method by dissolving one Aminoaminocarboxylate (I) directly in these solvents. When preparing the solution of the aminoaminocarbosylate in However, the first-mentioned case is obtained when using hydroxides of alkali metals or alkaline earth metals as Base M by neutralizing water or other low molecular weight substances and the substances with low molecular weight can react with the isocyanato radical, whereby the polymerization is disturbed or the component ζ is formed if the substance is with low molecular weight is water «In the latter case, this disadvantage does not occur, but it has other factors Disadvantages, such as B. The following: Increase in number the stages of the manufacturing process through the additional

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previous preparation of the aminoaminocarboxylate (I) and a generally lower solubility and poorer handling of the aminoaminocarboxylate (I) compared to the first-mentioned EaIl. In addition, a polymer electrolyte of the present invention is generally used in the form of an aqueous solution which can be directly prepared by the above-mentioned aqueous interfacial polymerization method. In the solution polymerization method, however, the aqueous solution can be prepared by only dissolving in water the polymer electrolyte previously isolated by precipitation in a non-solvent. When the object of the invention is to produce a molded product of the polymer electrolyte by the dry or measuring method, the solution polymerization method is advantageous in that the formed product can be easily obtained by evaporating the polar aprotic solvent or by extruding the polymer electrolyte solution into a layer. Solvent. A solvent-free polymerization can be carried out when the melting point of the aminoaminocarboxylate (I) is low or when its amine number (amine value) is small, that is to say, for example, when E ^ in the formula I contains any ether bond or when R- is selected from a very large number long-chain aliphatic hydrocarbon radical with a low melting point or polyether and polyester radicals. In the case of a high amine number, however, the solvent-free polymerization can be carried out by adding a filler which reacts neither with the isocyanato nor with the amino radicals. This filler is not the above-mentioned solvent, but a substance which does not necessarily need to dissolve the aminoaminocarboxylate (I) and the diisocyanate (II) and which contains them

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Can form polymer blend having satisfactory properties as a high molecular weight composite material. Typical examples of such diluent fillers that do not react with the diamine and diisocyanate include inorganic materials such as calcium carbonate, glass fibers, ceramic wool, rock wool _s fine gravel _s perlite, silicon dioxide, aluminum oxide, silicon dioxide, dballs _? Glass beads, barium sulfate and the like; organic materials such as wood, pulp, natural fibers or synthetic fibers, waste paper, fragments of plastics and the like; and metal powder such as iron powder, copper powder, aluminum powder and the like.

Even with a high number of areas, foamed products are produced by an exothermic reaction at high speed when the melting point of the aminoaminocarboxylate (I) is low. The solvent-free polymerization can be carried out by mixing the aminoaminocarboxylate (I) with a diisocyanate (II) in the presence or absence of any fillers, as required, by polymerizing them at a suitable temperature for a sufficient period of time and preferably by curing the resulting product at a higher temperature to further complete the polymerization. Although this solvent-free polymerization is advantageous in that a molded product can be obtained in one step can be formed, it has the disadvantage that it is difficult to prepare thermoplastic or soluble polymers .

Although the polymerization temperature in the above polymerization in a protic solvent (such as _e

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in aqueous interfacial polymerization), in polar aprotic solution polymerization and solvent-free polymerization depending on. Situation can vary, it is desirable that a relatively low temperature be used in the initial stage in each of these cases will. The reason is that the initial molecular weight of the polymer should be increased enough to be satisfactory Properties to be obtained in a substance with a high molecular weight by the generation of Urea bonds give priority, which is a consequence of the implementation the aminoaminocarboxylate (I) and if necessary Biamin (III) used with the diisocyanate (II) are. In the production of foamed products through Polymerization at high speed, however, the expansion is carried out by reducing the heat generation, which is a The consequence of the rapid release of the heat of polymerization is, used, regardless of the initial emp he at ur, so that the ■ crosslinking reaction can be caused as a side reaction, which has the consequence that the so-called initial or primary molecular weight is not very high, although it is sufficient for the properties of a foamed product. With increasing Polymerization temperature take the significant differences between the reactions of the amino radical, the water and the urea bond at the isocyanate residue, whereby the primary molecular weight hardly increases, and often can the component ζ increases when water is used or the cross-links increase. The addition of a catalyst can cause the significant differences in terms of the selective reactivity of the active protons, such as B. the amino residues, the urea residues and water, decrease with the isocyanato residue, depending on the type of used Catalyst. It is therefore desirable that the

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catalyst-free reaction is used in the initial stage of the polymerization and that the catalyst is added after the reaction between the amino and I socyanate ο residues has already been completed. The reason is that the catalyst-free reaction can often benefit from the normal amino radical>water> urea relationship in terms of reactivity towards the isocyanato radicals. The reaction of a small amount of remaining (remaining) isocyanato-residues can be accomplished by increasing the polymerization temperature at the end of polymerization, ie, to the Zeitpun k t for which the largest part of the isocyanato radicals has already been implemented. In this case, the above-mentioned competing reaction hardly if at all has a bad influence on the properties of the polymer, but on the contrary increases the molecular weight and eliminates the harmful influences which can be attributed to the remaining (residual) isocyanato residues. In general, the polymerization with protic solvents should preferably be carried out at a low temperature; the aprotic solution polymerization can of course be carried out at a relatively high temperature, and the solventless polymerization can be carried out within the range of both high and low temperatures.

Although the common features and advantages of the manufacturing method according to the invention are discussed in more detail above have been, the interfacial polymerization, Solution and solvent-free polymerization processes explained in more detail.

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Interfacial polymerization

The solvents used mainly in the interfacial polymerization process are used are water and organic solvents insoluble in water. With the latter it can be any organic solvent that dissolves diisocyanates (II) and with the isocyanato radicals do not react or react only very slowly, e.g. B. aliphatic hydrocarbons or the halides or sulfides thereof, such as cyclohexane, chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, tetrachlorethylene, carbon disulfide and the same; as well as aromatic hydrocarbons or the halides or the nitro derivatives thereof, such as Benzene, xylene, chlorobenzene, dichlorobenzene, nitrobenzene and the like, but it should be noted that the The compounds given above are only examples, to which the invention is not restricted. Strictly speaking this interfacial polymerization should be an interfacial polyaddition reaction are designated in contrast to the so-called interfacial polycondensation reaction in which The conventional Schotten-Baumann reaction is applied * One of the biggest differences between these two reactions is that in the interfacial polycondensation reaction the aqueous system for neutralization Alkali is added to remove the hydrogen chloride or other low molecular weight by-products and to shift the equilibrium of the reaction in the direction of polymer formation. Typical examples of this reaction, which is carried out with the addition of alkali are the production of a polyamide by interfacial polycondensation reaction of dibasic acid chloride and diamine, the production of polyurethane by interfacial

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Polycondensation reaction of dichloroic acid ester and Diamine or the production of a polyvinyl ester by the interfacial polycondensation reaction of a dibasic Acid chloride with, for example, bisphenol «The interfacial polycondensation reaction is an equilibrium reaction in which the polymerization only proceeds when the Low molecular weight by-products are removed, while in the interfacial polyaddition reaction, none such equilibrium reaction is that no alkali needs to be added because there are no low molecular weight products are formed. During the polymerization, the aminoaminocarboxylate (I) and the diamine (III) (if necessary) dissolved in water while the diisocyanate (II) is dissolved in the above-mentioned organic solvent, the is not miscible with water Aminoaminocarboxylate (I) can also be prepared by Dissolve the aminoaminocarboxylic acid and the base M in the polar one Solvent for neutralization rather than by directly dissolving the aminoaminocarboxylate (I) in the polar solvent.

Although the concentrations of the reactants in the solvents can be selected quite arbitrarily, it is advisable that the concentrations of aminoaminocarboxylate (I) are relatively high for the production of carboxylate polyurea with a high electrical charge density. As a rule, these concentrations have a maximum limit to such a value that the polymer solution or emulsion formed can still be stirred. A higher viscosity can however, the polymerization may be delayed or uneven polymerization may occur, so that the appropriate Concentration within the range of 0.1 to 40,

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can preferably be from 1 to 30%.

Although the maximum limit of the polymerization temperature is 10O ⁰ C, because an aqueous system is used, the actual polymerization can be carried out below the boiling point of a specific organic solvent when this solvent boils at a temperature below 100 ^0C. If the temperature is increased as indicated above, then the z-components of the carboxylate polyurea are greatly increased as a result of the reaction of the water with the diisocyanate (II) and the x-components, i. "H. the carboxylate components, may be decreased or hydrolysis may occur. Therefore it is advisable to carry out polymerization generally at about 6O ⁰ C or below. Although the minimum limit of the polymerization temperature only needs to be higher than the freezing temperature of the aqueous solution, it often falls below ⁰ ° C. as a result of the freezing point depression which is due to the presence of the aminoaminocarboxylate (I) and the diamine (III). However, if the freezing point of the organic solvent is above O ⁰ C, as is the case with benzene, for example, and if the concentration of the solution is too low to bring about a freezing point depression to below O ⁰ C, then the polymerization should take place at a temperature above O ⁰ C can be carried out. It follows that the main polymerization should preferably be up to 6O ⁰ C, more preferably from 0 to 35 ° C, carried out at a temperature within the range from the freezing point of the polymerization system.

Although the carboxylate polyurea of the present invention is satisfactory high molecular properties according to the

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Main polymerization reaction can be produced in which the reaction of most of the isocyanato radicals present is complete (finished), it is desirable that curing is finally carried out at a slightly higher polymerization temperature in order to reduce the reaction of the low Amounts of remaining (remaining) isocyanato residues to be completed as indicated above. If you do this, so is usually heated to a temperature that is around 5 "up 30 ° C higher than the main polymerization temperature « In addition, as stated above, the polymerization can be carried out by adding catalysts such as tin (II) octoate and IT-ethylmorpholine, which the reaction of the amino radicals with the isocyanato radicals selectively accelerate and hardly any influence on the reaction between the isocyanato radicals and Have water, be accelerated. Although these catalysts are added in the initial stage of the main polymerization reaction it is most advisable to add them at the end of the main polymerization, i. e. at the time when most of the isocyanato residues have already been completely reacted, and then the polymerization at the same Continue temperature in order to preferably avoid the side reactions already mentioned above. In the production of Polymers with intentionally increased ζ components, in water insoluble polymers or crosslinked polymers, the end purpose can be achieved by doing in the initial stage the main polymerization reaction triethylenediamine, tetramethyl-1,3-butanediamine, Dibutyltin dilaurate or other catalysts that promote the reaction between the isocyanato radicals and affect water, as well as adding the above-mentioned catalysts.

The reaction product obtained in this way can, for example, according to

809835/0770

-MO-

isolated or purified using the procedures described below. Since there is hardly any carboxylate polyurea in the organic If the solvent phase is present because of its high polarity, the aqueous phase containing the product can be obtained are by separating and removing the organic solvent phase by decanting or by means of a Separating funnel when the aqueous and organic solvent phases are separated from each other in the form of layers will. Although the aqueous solution of the carboxylate polyurea by evaporation of some residual organic Solvent can be freed and used directly as a product can be a carboxylate polyurea if necessary, can also be isolated by precipitation, as explained below. If any insoluble in water Polymer is present, it only needs to be isolated beforehand by filtration. When the reaction mixture is in shape an emulsion, suspension, paste or cream is present which prohibits the above-mentioned separation of layers, the organic Solvent is removed by heating the mixture under reduced pressure and then the above treatment is carried out carried out. If a uniform phase cannot be achieved at all, the carboxylate polyurea can by evaporating a suitable amount of water and the organic solvent to concentrate the reaction mixture and then adding the concentrate obtained in this way to a water-soluble solvent which, however, has the Carboxylate polyurea cannot dissolve, can be isolated to achieve precipitation. Since the isolated substance both may contain water-soluble components as well as water-insoluble components, one can only consist of the water-soluble component existing aqueous solution can be obtained by redissolving these two components in water and the

809835/0 770

insoluble fraction filtered off in order to separate these components from each other. Although the resulting solution can be used directly as the end product, as mentioned above, the carboxylate polyurea can also be isolated by precipitation if necessary. In the case of precipitation, the aqueous solution can be added directly to the precipitation solvent or, in another method, the aqueous solution is dried until it is free of water and then it is dissolved in another solvent, e.g. B. in polar aprotic solvents, as they are used in the solution polymerization, which is described below, and in polar protic solvents,. Wie z. B. alcohols, formic acid, formamide, m-cresol and the like, $ e of the type of carboxylate polyurea, dissolved, the resulting solution being added to a precipitation solvent to achieve precipitation. The precipitation solvent can be selected from nitriles, e.g. B. acetonitrile and propionitrile, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether, dioxane and tetrahydrofuran, and esters such as ethyl acetate, can be selected. The precipitation solvent, however, is not limited to the above-mentioned substances, but also includes solvents which have permanent dipoles which can hardly rotate freely and which cannot or can hardly dissolve the carboxylate polyurea. Spruce polar solvents or polar solvents with freely rotating chemical bonds tend to form gummy or oily substances.

Solution polymerization

In solution polymerization, polar are aprotic

809835/0 770

Solvent preferred because the electrolyte, i. H. the Carboxylate polyurea, can hardly be dissolved in solvents with a low polarity and because aprotic solvents, which do not have active hydrogen atoms are required to initiate the reaction between the isocyanato groups and to keep the solvent to a minimum. Such aprotic solvents include tertiary amides, such as Ν, ΪΤ-dimethylformamide, N, N ~ dimethylacetamide and N-methylpyrrolidone; aprotic organic sulfur oxides such as dimethyl sulfoxide; and [thiester of phosphoric acid, such as i-triethyl phosphate and tri-n-butyl phosphate. Aminoaminocarboxylate (I) with a low electric charge density or a lithium salt thereof can, however, also be used in the above-mentioned polar solvents can hardly be resolved. In such a case, the solubility can be increased by adding some electrolytes that are compatible with the Diisocyanate (II) do not react, but dissolve in the polar solvents, can be improved. Such an electrolyte can be selected from salts such as fluorides, chlorides, perchlorates and nitrates of alkali metals such as z. B. lithium, sodium and potassium; Zinc chloride; Mercury chloride, Alkaline earth metal alcoholates, such as lithium methylate, Sodium methylate and potassium ethylate; Salts such as a halide, perchlorate, tetrafluoroborate, nitrate, acetate and sulfonate of tetraalkylammonium; Tetraaryl borates such as B. Tetraphenylborate.

Although the aminoaminocarboxylate (I) is dissolved in the above-mentioned polar solvent in the polymerization, it may be used if necessary any of the above electrolytes can be added as solubilizing agents. If does so, the electrolyte solubilizing agent is added at a concentration that is below it

809835/0770

Saturation solubility is in the polar solvent, but the addition of a small amount of solubilizing agent may sufficient because its solubility is usually low. If necessary, a diamine (III) of the solution of the Aminoaminocarboxylate (I) can be added. The appropriate solution of the aminoaminocarboxylate (I) can also be prepared by dissolving the aminoaminocarboxylic acid and the base M in the polar solvent for neutralization in place of the directly dissolving the aminoaminocarboxylate (I) in the polar one Solvent. In this case, however, water may sometimes be generated upon neutralization, as stated above. The water can be removed by adding a conventional de-hydrating agent mixed with the aminoaminocarboxylate (I), the diisocyanate (II) and the diamine (III) and the carboxylate polyurea do not react. A such dehydrating agent can be selected, for example, from the group sodium sulfate, magnesium sulfate, Calcium sulfate, copper sulfate, aluminum sulfate, aluminum oxide and silica gel. Although the diisocyanate (II) can be added directly to the solution, it can cause a sudden exotherm React when the concentration is high or the basicity of the amine component is strong. This can be avoided are made by diluting the diisocyanate (II) with the polar solvent and gradually adding it to the Solution of the amine component. Although the polymerization can be carried out in air, it is preferably carried out in a dried (dehumidified) inert gas atmosphere carried out to denaturation of the diisocyanate, the aminoaminocarboxylate (I) and / or the diamine (III) to be kept to a minimum by means of carbon dioxide and water in the air.

Although the polymerization temperature has any value

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above the freezing point and below the boiling point of the polymerization system, higher temperatures tend to form the abovementioned biuret bonds as a result of the reaction between the urea bonds and the isocyanato radicals and as a result of the accompanying Meben reactions, such as. B. a crosslinking reaction. Therefore, the polymerization is usually at a temperature below 200 ⁰ C should preferably be above the freezing point up to 100 ⁰ C is performed. In practice, the first stage of the polymerization is carried out at a relatively low temperature, for example at normal temperature (20 ^° C.), in order to keep the side reactions to a minimum, and the polymerization of the second stage is started after most of the isocyanato residues has been implemented. In the second stage polymerization, the reaction temperature may be practically the same as that of the first stage, although the polymerization reaction can be further completed by adding a catalyst to accelerate the reaction between the above-mentioned isocyanato and amino groups. If the second polymerization stage still does not produce a polymer with a high molecular weight, with a small amount of isocyanato radicals remaining, it is advantageous to carry out the third polymerization stage at a temperature which is 5 to 100 ^° C. higher than that of the first and the first second stage. Not all of these three polymerization stages are required; often the first stage alone is sufficient when the rate of polymerization is high or when aromatic diisocyanate and aliphatic diamine reactants react with one another or when a high concentration of the reactants is used to carry out the reaction. The first polymerization stage can be followed directly by the third stage or the second polymerization stage

809835/0770

_{be carried out first in the case of a very low polymerization rate o} In a reaction system with a high polymerization rate, however, from the standpoint of side reactions, it is not desirable to start the second or third polymerization stage omitting the first polymerization stage, o

When the polymerization is carried out under the above-mentioned conditions, it is completed within a period of time which is within the range of a few minutes to about 10 hours _o Although the reactant concentration may be any value that allows stirring or kneading of the reaction system , xcLrd by a low concentration of the polymerization deferrers ~ siege or the yield decreased too high a concentration has the advantage that it increases the rate of polymerization, it has ge ^ och but also the smiling part that side reactions, such as, _e B ₀ a crosslinking reaction , occur which result in impure polymer masses _o The polymerization should therefore generally be carried out with a reactant concentration of 1 to 50%, preferably 5 to 30%.

Although a solution of the Carboxylatpolyharnstoffs thereby obtained i-Jerden so as obtained used depending on the purpose can, the polymer may be but even isolated by precipitation using the above Ausfällungslösungsmittels _o In addition, by heating and evaporation of the solvent (dry process) Films can be made, or films or fibers can be made by pouring the solution into a non-solvent (custom process), _{or the like}

809835/07

Solvent-free polymerisation

The solvent-free polymerization method is applicable to the cases where the aminoaminocarboxylate (I) has a low melting point or its amine number is small, or a mixture of the aminoaminocarboxylate and the diamine (III) has a low melting point or a small amine number, as well as mixtures, which contain the above fillers. In these cases, the polymerization is generally carried out immediately after the starting materials have been mixed and after the mixture has been poured or poured into a suitable container or mold. Although catalysts are hardly required because the rate of polymerization tends to be high, they should be used appropriately when fillers are used for dilution. The polymerization is usually carried out at about normal temperature, although cooling or heating can also be carried out if necessary. After the polymerization is almost over, the reaction system should be heated to a temperature higher than the polymerization temperature of the first stage for an appropriate period of time to further stabilize the properties of the polymer. The preferred! Temperature for the first stage polymerization is generally carried out at O to 10O ⁰ G, while the so-called curing temperature is in the second stage within the range of 50 to 200 ⁰ C. The polymerization time varies depending on the polymerization temperature, filler and reactant within the range of 30 minutes to 30 hours for the first stage polymerization and within the range of 0 to 30 hours for the curing reaction of the second stage.

809835/0770

The carboxylate polyurea of the present invention has as a polymer electrolyte the following excellent properties;

(a) It is readily soluble in water or has hydrophilic properties,

(b) it can be flocculated,

(c) its surface tension never changes _s

(d) It has good moisture and water absorption properties on,

(e) it has good antistatic properties,

(f) it is ionizable,

(g) it has the ability to form chelates with metals, (h) it is ion-exchangeable,

(i) it has a buffer effect,

(d) Although it has a polar residue, it has low ones dielectric properties on, and

(k) it is safe from organisms.

All of these properties, with the exception of property (k), are entirely due to the characteristic effects, which are a consequence of the presence of the x component; some properties are even more pronounced in one higher rate of x component and others show an improvement over conventional polyureas or others Components that are caused by the addition of the x-component.

To utilize the above-mentioned advantageous properties, the polyurea according to the invention can be used for

809835/0770

a wide variety of applications can be used, for. B. as an antistatic agent, as a dye fixative, as a flocculant, as a sensitizer, as a light-sensitive agent, as an auxiliary for printing inks or paints, as an ion exchange resin, as an adsorbent, as a chelating agent, in electrodeposition paints, in water-soluble adhesives, in reactive paints, in harmless agricultural ones Chemicals, cosmetic materials, dielectrics, oxidizing and reducing agents, pH control agents, Soil conditioning agents and the like.

The invention is illustrated in more detail by the following examples, without, however, being restricted thereto. In these examples the diamines with the remainder R ^ are only selected from the aliphatic, aliphatic-substituted aromatic and aromatic diamines and the diisocyanates with the remainder R, are only selected from the aliphatic, aliphatic-substituted aromatic and aromatic diisocyanates According to the invention it was found that for the reactivity of these diamines the following relationship applies: aliphatic> aromatic, while for reactivity of the diisocyanates the following relationship applies: aromatic > Aliphatic, the reactivity of the compounds of the other groups being between that of the aromatic and of the aliphatic compounds.

809835/0770

Examples T - 5

5.00 g (0.038 mol) of N- (2-Cürboxyäthyl) ethylenediamine (F * 130 bis 136 C, hereinafter abbreviated to CEED) and a solution of 1.44 g (θ, Ο3ό mol) sodium hydroxide (this corresponds to the equivalent, calculated from the measured value of the acid equivalent of CEED) in the amount given in Table I below degassed distilled water was poured into a with a dropping funnel with a side arm that acted as a nitrogen inlet, a cooler that acted as a nitrogen outlet, a thermometer 4-neck pear-shaped detachable flask (capacity 200 ml) equipped with a stirrer and the contents were introduced purged with nitrogen and stirred while the flask in one The water bath was kept at 20.degree. C. An amount of diisocyanate which corresponded to the Xsocyanatorest / Aminorest index that was measured from the The value of the base equivalent of CEED was calculated and is given in the following Table I, was in the The following table I dissolved and the amount of methylene chloride given the resulting solution gradually passed through the dropping funnel added dropwise into the stirred solution. After the end of the dropping, the solution was used to carry out the reaction the same temperature and then further stirred at a higher temperature. The reaction product was separated into three layers; an aqueous phase, an organic phase and a fraction that is not soluble in any of these phases. After the insoluble fraction had been filtered off and separated, the aqueous phase and the organic phase by means of a separating funnel or separated by a centrifuge. The aqueous phase was concentrated or evaporated under reduced pressure and then in

Dissolved methanol. The resulting solution became a fully stirred nonsolvent for the precipitate added and a colorless powder was obtained. After evaporation of the solvent in the organic phase An unreacted residue of diisocyanate was obtained in vacuo. In the following Table I, the measurement results are shown in with respect to the yield, the softening point and the intrinsic viscosity (Basic molar viscosity).

Referring to Example 1, the following is the procedure for analyzing the water-soluble polymer obtained thereby. Dos water-soluble polymers asymmetric stretching vibrations of carboxylate within the range of 1580 to 1560 cm of the infrared absorption spectrum, symmetrical stretching vibrations of the carboxylate within the range from 1410 to 1400 cm, an absorption of the amide I. at Ί 040 to 1020 cm and an absorption of the amide II 1550 to 1530 a on. In addition, if this arose Polymers was dissolved in heavy water and the nuclear magnetic resonance spectra were determined, chemical shifts in the O fourth at α to d of the formula (E) given below

OO O

Si I

S I I

—BIHCH (CH) .CHpNC-KCH ₉ CH »NC} [-NCH ₉ (CH) CH HC]

da d ^{Η h} c ~; 1 ^Π dad ^H

^G V ^h 2

Y2_ a. COO Na '

as follows: α = 1.10 to Ί, άϋ ppm; b = 2.30 to 2.44 ppm; and c-id = 2.96 to 3.50 ppm. Dcbsi were multiplet signals. To get the components υ υηό ζ in the formula (Ε).

808835 / Q770

the water-soluble polymer was dissolved in water and titrated with a 0.1 η hydrochloric acid solution to the carboxylate equivalent and the component amount fraction of χ was obtained from the following equation

measured value of the carboxylate equivalent of the polymer

χ = calculated value of the carboxylate equivalent of structure χ

The measured value and the calculated VJert were

-3 carboxylate equivalents of the water-soluble polymer 2.49 χ 10

-3
Eq / g and 3.10 x 10 eq / g, respectively, so that the polymer was found to be a carboxylate polyurea having a composition given by χ = 0.805 and y = 0 »A small amount of the water-insoluble one Portion had a composition given by y = 0 and ζ> Γ7χ.

The water-soluble polymers of Examples 2 to 5 were carboxylate polyureas with a composition given by y = 0 and 77 * -100 x / (x + z) < -96, as indicated in Table I below "A small amount of the water-insoluble fraction had a composition that is given by y = 0 and ζ, \ >>x."

When the aqueous solutions of the polymers were added to solutions of the salts of copper, iron, cobalt and manganese, a Precipitation, showing that the polymers have a chelating ability had.

809835/0770

A 48 μm thick film was produced by dissolving the water-soluble polymer of Example 3 in methanol, pouring the resulting solution onto a Teflon-coated iron plate and drying at 40 to 50 ° C. The insulation resistance of this film was determined by measuring the film on the super ultrasonic meter, model SM-l0 _f and an ultrasonic meter, model SM-5E (both products from Toa Denpa Kogyo Co., Ltd.), in an atmosphere of 21 + 1 C and 65 + 5 % relative humidity ( RH) and read off the values after operating the measuring devices for 1 minute. It was found that the surface resistivity and the volume resistivity of the film were 1.4 to 2.1 10 ohms and 1.5 to 2.3 χ 10 Ω · cm at 100 V, a sufficiently low electrical resistance. In addition, a similar film placed on a grounded aluminum plate was applied with a voltage of 15 KV for 5 seconds by using the charger, model KTB-5 (manufactured by Kasuga Denki Co., Ltd.) measured by electrostatics Charge Meter, model KQ-431 (from Kasuga Denki), and the amount of charge turned out to be too small for detection.

A flocculation test for the water-soluble polymer of Example 3 was carried out. For the liquid were about 2300 ppm (pH 7) of a barium sulfate suspension in water is used. This suspension was placed in a sealed 250 ml measuring cylinder introduced and it was a 0.1 wt .- JSige solution of the water-soluble Polymers added. After turning the graduated cylinder 10 times

809835/0770

it was allowed to stand and the amount required to achieve a constant sedimentation volume of the flakes Time was determined. The sedimentation began immediately after the measuring cylinder was left to stand, and it was finished within 3 minutes regardless of the fluctuations in the amount of polymer added - 3,6 and 12 ppm - and there was a cohesive effect.

The same flocculation test was carried out with the water soluble Polymers of Example 4 carried out and the greatest effect was obtained with an addition of 3 ppm, with the cohesive sedimentation finished within 2 minutes.

To determine the influence on the surface activity of the water-soluble polymer of Example 4 was the surface tension measured at varying concentrations of the polymer in water. The Denui Surface & Interfacial was used for this Tension Meter (available from Shimazu Seisaku-sho Co., Ltd.) at a liquid temperature of 19.0 ° C It has been found that the surface tension varies with the Concentrations hardly changed, as indicated below.

concentration
(Weight -f.) 70.6 j
I.
5xlO ~ ⁵ j 5 * 10 ~ ⁴ 69.1 5xlO ~ ³ 5x10 ² 5XlO " ¹ . surfaces
tension
(dyn / cm) 68.9. 69.2 70.6 67.0

08835/07? ©

Table I - (I) Conditions and Results of Synthesis of Carboxylate Polyurea

OO O (O CO CO

example Diiso-
cyanate:
g (mole) index -solution milk (m £) Methylene
chloride Reaction temp. and reaction
time ( ⁰ CZmLn) Yield {%) 50/150 56.0 in water
more insoluble
_ Ar, + «ί 1 1 HMDI (i)
5.92
(0.035) 1.0 water 50 A drop-
to lead water soluble
Stirring
■ · . · »·", · Ι - 40/30 92.2 . .ητβί.ι ι
6.8 2 HMDI
7.10
(0.042) 1.2 70 40 20/30 20/40 40/150 76.9 1.7 ι
ί
3 HMDI
8.29
(0.049) 1.4 50 30th 20/7 25/140 40/30 82.9 very
low ^v 4th MDI (ii)
April 9
(0.036) 1.0 30th 50 20/8 20/170 40/50 66.6 9.0 5 2.4 TDI (Ui)
8.59
(0.049) 1.4 50 50 20/40 20/30 12.7 50 20/32 20/217

Footnotes: _ (i) HMDI = hexane -1,6-diisocyanaf

(ii) MDI = diphenylinethane -4,4 '-diisocyanate (iii) 2,4-TDI = 1-methylbenzene -2,4-diisocyanate (iv) intrinsic viscosity, was at one concentration from 0 .125g / 25mÄ. measured

* V3 * Catalyst-free polymerization CJO

in the examples 1-5 ι C ^

OO «

Table I- (2)

CD O CO 00 CO cn

example Softening point in water υ η
■ Soluble An
part Intrxnsio viscosity
(30 ⁰ C, m-cresol)
of the water-soluble
"Share '< ^iv) Precipitation solution
middle Remarks
^ gen 1 water-soluble
lean appearance
+ Pi Ί 215-220 0.143 Precipitation by addition
the methanol solution of the
Polymers to acetone x = 0.805
(water-soluble
Iicher An
part) 2 100-110 164-210. 0.216 Il x = 0.771
(water-
rel. to
te i i) 3 100-120 - 0.334 H x = 0.771
(water-
rel. to
part) 4th 169-184 260-300 0.111 Precipitation by addition
an aqueous solution of
Polymers to Acetonitrile ' x = 0.959
(water
sol 1. An
part) 5 183-188 234-247 0.105 Precipitation by addition
a methanol solution of
Polvmeren to acetonitrile x = 0.819
(water
iös 1. An
partV 230-235

CJI

Examples 6-11

Using the same apparatus as in Example 1, the amounts shown in Table II below were obtained N- (2-carboxyethyl) hexamethylenediamine (m.p. 107 - Π3 C, hereinafter abbreviated as CEHD) and a solution of such an amount of sodium hydroxide as the equivalent that was calculated from the measured value of the acid equivalent of CEHD, in the amount given in Table II below Degassed distilled water is introduced into the flask, purged with nitrogen, and stirred while the flask is in the water bath was kept at 20 C. An amount of diisocyanate corresponding to the index derived from the measured value of the base equivalent was calculated by CEHD and shown in the following Table II, was dissolved in methylene chloride and the resulting Solution was slowly added dropwise through the dropping funnel to the stirred solution. After the completion of the dropping, the solution became for carrying out the reaction at such a temperature for a period of time as indicated in Table II below is touched. The reaction product was separated into three layers: an aqueous phase, an organic phase and a portion which was not soluble in any of these phases. After the insoluble Fraction had been filtered off and separated off, the aqueous phase and the organic phase were separated by means of a separatory funnel or separated from each other by means of a centrifuge and their respective solvents were evaporated under reduced pressure. The water-soluble portion was dissolved in methanol, and the resulting solution was used to cause precipitation

809835/0770

added to a completely stirred non-solvent and a colorless powder was obtained. The following Table II shows the measurement results relating to the yield, the softening point and the intrinsic viscosity.

From the infrared absorption spectra, the nuclear magnetic resonance « spectra and the titrated value of the base equivalent showed that the water-soluble polymers carboxylate polyureas with one through y = 0 and 70 "^. 10O x / (x + z) < 90 given composition, as given in the following Table II, were ο The ones in water insoluble fraction in Examples 6 to Π had a composition as indicated by y = 0 and z>? χ is given »

The same flocculation test as done with the polymer of the example 3 was carried out with the water-soluble polymers of Examples 6 to 8 and the greatest effect was achieved in all cases with an addition of 9.0 ppm, the sedimentation being completed within 2 minutes.

0.1 wt. -% - i ge aqueous solutions of the water-soluble polymers of Examples 9 and 10 were subjected to the same test that had been carried out with the polymer of Example 3, and the greatest effects were obtained with an addition of 3.0 ppm, the sedimentation times in Examples 9 and 10 were 4 and 3 minutes, respectively.

When an aqueous solution of the water-soluble polymer of the example 11 was added to an aqueous solution of a transition metal salt, a precipitate was formed which had the ability to form chelates

809835 / Ό770

showed. The water-insoluble polymers of Examples 11 to 11 resulted in effective flocculation of an organometallic Compound, such as tin (II) octoate.

809835/0770

Table II - (l) Conditions and results of the synthesis of the carboxylate polyurea

OO O CO OO Ct) cn

example CEHD
g (mole) Diiso-
cyanate:
g (mole) - sodium index Solvent ^) Methylene
chloride Renktionjstemp. ^{and ReQ} l <- |
tion time x ^ö c / min) | stir 40/60 6th 7:00
(0.037) HMDI
5.76
(0.034) hydroxide:
g (mole) 1.0 water 50 Dropping
stir 20/65 4 0/4 5 7th 5.00
(0.027) HMDI
6.59
(0.039) 1.28
(0.032) 1.4 100 40 20/60 20/128 40/40 8th 4.00
(0.021) MDI
6.28
(0.025) 0.91
(0.023) 1.6 50 40 20/15 20/157 40/30 i
I. 9 5.00
(0.027) MDI
6.86
(0.027) 0.73
(0.018) 1.0 . 50 50 20/11 20/30 40/30 10 2.4 TDI
5.97
(0.034) 0.91
(0.023) 1.4 70 ' 50 20/15 20/250 40/30 11 1.4 70 50 20/25 20/280 70 20/20

Cn

example Yield {%). s- in water
more insoluble
_An + Pi 1 Table II - (2) Softening point 225-263 Intrinsic
viscosity
(30 ⁰ C, m-cresol)
the water soluble!
Proportion Precipitation solution
middle
1 Remarks 6th water
Ii c her
proportion of 39.0 r water! in water
.solubleqr _soluble _
Share my share 244-258 0.195 Precipitation through
Adding a 'metha
nol solution of the poly
mers to acetone x = 0.773
(more water soluble
Proportion of)
insoluble part
ninh = 0.5 60 50.5 16.0 120-130 200-217 0.202 Precipitation through
Adding a metha
nol solution of the poly
mers to aceto
nitrile x = 0.735
(more water soluble.
Proportion of) 8th 73.9 29.1 135-140 125-238 0.219 x = 0.784
(more water soluble
•Proportion of)
insoluble part
nmh = o.35O co
CD
CO 9 69.1 24.4 149-151 206-215 0.139 x = 0.737
(more water soluble
Proportion of) 835/0770 10 77.0 44.1 181-187 225-227 0.171 ■ x = 0.862
(more water soluble
Proportion of) 11 42.1 26.1 210-215 0.175 x = 0.888
(more water soluble
Proportion of) 67.4 212-218

Examples 12-17

Using the same device as in Example 1 the amount of N- (2-carboxyethyl) -p-xylylenediamine (Fo 178.0 to 180.5 ° C., below abbreviated to CEXD) and a solution of an amount of sodium hydroxide equal to the equivalent obtained from the measured value of the acid equivalent of CEXD was calculated, degassed in the amount given in Table III below Distilled water is added to the flask, purged with nitrogen and stirred while the flask is in the water bath at 20 ° C was held. An amount of diisocyanate corresponding to the index calculated from the measured value of the base equivalent of CEXD and shown in Table III below, was dissolved in methylene chloride and the resulting solution was through the dropping funnel slowly dripped into the stirred solution. After the completion of the dropping, the solution was used to carry out the reaction within the range shown in Table III below The reaction product was stirred for a period of time at this temperature was separated into three layers: an aqueous layer, an organic phase and a portion that is not in any of these phases was soluble, or it was in the form of an emulsion »In the first-mentioned state, the product was the same Way as in Examples 1 to 11 separated »In the last The state mentioned above was the emulsion by means of the centrifuge broken, separated into three layers or reprecipitated directly in the non-solvent and then in the water-soluble ones and water-insoluble fractions "The following Table III shows the measured results with respect to

835/0770

the yield, the softening point and the intrinsic viscosity the colorless powder obtained by precipitation and the insoluble part.

From the infrared absorption spectra, the nuclear magnetic resonance spectra and the titrated value for the base equivalent were found that the water-soluble polymers thereby obtained Were carboxylate polyureas having a composition given by y = 0 and 65 ^ -x / (x + z) <97, as in the following Table III given. The water-insoluble portion in Examples 12 to 17 had a composition indicated by y = 0 and z »x is given.

It was the same flocculation test as it was with the polymer of Example 3 had been carried out with the water-soluble polymers of Examples 12 to 14 and they showed all exhibited good flocculant properties, the greatest effect being obtained with the water-soluble polymer of Example 15. The time required to equilibrate the sedimentation rate was 2.5 with an addition of 3 ppm Minutes. Of 250 ml of the suspension, 215 ml became clear 30 minutes after the whole suspension was allowed to stand while only 15 ml became clear 30 minutes after the whole suspension had been left to stand if no water-soluble polymer was added became.

The water-soluble polymer of Example 14 was applied to the the same way as in Example 3, a film with a thickness of 55 μm manufactured. When measured under the same conditions as in Example 3, the volume resistivity of the film was found

809335/0770

1.6 χ ΙΟ ¹³ ohm χ cm at TOO V and 6.8 χ ΙΟ ¹² ohm χ cm at 250 V.

13 and the specific surface resistance was 1.6 χ IO

Ohm at 100 V, 6.3 χ 10 Ohm at 250 V and 4.3 χ ΙΟ ¹² Ohm at 500 V, so it was 10 to 10 lower than the electrical resistance of conventional polymers «

From the water-soluble polymer of Example Io, the the same way as in Example 3 a 62 μm thick film was produced » When the measurement was carried out under the same conditions as in Example 3, the volume resistivity of the film was

4.4 χ 10 ohm χ cm at 100 V, 6.1 χ 10 ohm χ cm at 250 V and

1.5 χ 10 ohms χ cm at 500 V and the specific surface resistance was 2.6 χ 10 ohms at 100 V, 3.7 χ ΙΟ ^1] ohms at 250 V and 9.5 χ 10 ¹¹ ohms at 500 V,

When aqueous solutions of the water-soluble polymers of Examples 15 and 17 are added to an aqueous solution of the transition metal salt this led to precipitation, which reduced their chelating ability shows.

809835/0770

Table III - ("I) Conditions and Results of the Synthesis of the Carboxylate Polyurea

g (mole) Diiso-
cyanate.:
g (: tol) sodium
hydroxide:
g M.ol) index Solvent, _ "»
tfii ^{(m ]} Methylene -
chloride· Reaction temp. and Reak
tion time (° C / roin) stir 40/30 i
1 40/30 example 6:00 am
(0.029) HMDI
4.62
(0.028) 1.23
(0.031) 1.0 water 50 Dropping
stir 20/30 'I.
20/120 ^; 40/30 40/30 12th
I.
i 5.00
(0.024) HMDI
5.39
(0.032) 1.02
(0.025) 1.2 100 40 20/60 20/130 40/40 13th MDI
5.88
(0.023) 1.4 40 30th 20/15 20/30 40/50 14th MDI
6.88
(0.028) 1.0 30th 50 20/8 20/300 15th 2.4 TDI
5.59
(0.032) 1.2 50 ' 50 20/32 20/230 16 1.4 50 50 20/25 17th 50 20/20

example Yield (%) 7.6 Softening
point ( ⁰ C) in water
r insoluble Table Hl - (2 ) Precipitation solution
middle Remarks 12th Wasserlöd- in Wassei
dear ArI- insoluble-
■ te ¹ · ¹ ·! Rather share 7.4 water-,
soluble
proportion of 233-238 Intrinsic
Viscosity
(3O ⁰ C, m-ztöresol)
water soluble '
proportion of Precipitation through
Addition of a mead
fulfillment of the poly
mers to acetonitrile X = 0.809
(more water soluble
_L share). ■ 13th 58.0 7.3 131-134 170-180 0.153 Precipitation through
Adding a metha
nol solution of poly =
mers to acetone x = 0.841
(more water soluble
Proportion of) · εσ
O
co
CO
£ *>
cn
O
-J
-a
Q • 14 79.4 20.2 148-152 167-205 0.314 Precipitation through
Addition of a metha = -
nol solution of the poly
mers to acetonitrile x = 0.8 88
(more water soluble
Proportion of) 15th 73.0 34.5 163-168 235-240 0.450 X = O.913
(more water soluble
Share) ■ 16 30.5 20.5 230-234 235-240 0.191 x = 0.962
(more water soluble
L share) 17th 62.7 245-250 215-228 0.204 x = 0.664
(more water soluble
Proportion of) 65.0 182-188 0.136

Example T8

Using the same apparatus as in Example 1, 8.00 g (0.0395 mol) of N- (2-methyl-2-carboxyethyl) hexamethylenediamine (m.p. 147.0 to 148.6 C) and a solution of 1, 58 g (0.0396 mol) of sodium hydroxide in 50 ml of degassed distilled water was added to the flask, purged with nitrogen, and stirred while the flask was kept in a water bath at 30 ° C. A solution of 6.65 g (0.0396 mol) of hexane-1,6-diisocyanate in 50 ml of carbon tetrachloride was added dropwise through the dropping funnel to the stirred solution over a period of 38 minutes. Immediately after completion of the dropping were 0.1 wt -.% (Based on the total weight of the content) of tin (II) octoate was added to the solution, the more to carry out reaction at 142 minutes at 30 C and then for 120 minutes 40 C was stirred. After the completion of the reaction, the product, which was in an emulsion state, was separated into an aqueous phase, an organic phase and an insoluble portion by means of the centrifuge. A solution of the water-soluble fraction was added to the completely stirred non-solvent acetone for precipitation, and a practically colorless, thread-like polymer was obtained. From the infrared absorption spectra, the nuclear magnetic resonance spectra and the titrated value of the base equivalent, it was found that the water-soluble polymer thus obtained was a carboxylate polyurea having a composition given by y = 0 and χ = 0.605. The water-insoluble fraction had a composition which was given by y = 0 and z »x.

809835/0770

The measured values relating to the yield, the softening point and the intrinsic viscosity of the water-soluble polymer were 69.4 %, 143.0 to 148.0 ° C and 0.417 (η . / M-cresol), respectively.

A 0.11 mm thick film was prepared from this polymer in the same manner as in Example 3. When measuring under the the same conditions as in Example 3 was the specific

13 Volume resistance of the film 2.0 10 0hm χ cm at 100 V, 5 χ 10 0hm χ cm at 250 V, 4.7 x 10 0hm χ cm at 500 V and

12th
1.6 10 0hm χ cm at 1000 V, and the specific surface

12th
resistance was 6.0 to 8.3 χ 10 ohms at 100 V, 250 V, 500 V and 1000 V. The under the same conditions as in

The amount of charge measured in Example 3 was 3.5 e.s.u. / cm.

Example 19

Using the same apparatus as in Example 1, 8.00 g (0.0395 mol) of N- (2-methyl-2-carboxyethyl) hexamethylenediamine and a solution of 1.58 g (0.0396 mol) of sodium hydroxide in 50 ml degassed distilled water was introduced into the flask, purged with nitrogen, and stirred while the flask was kept in a water bath at 30 ° C. A solution of 9.89 g (0.0396 mol) of diphenylmethane-4,4'-diisocyanate in 50 ml of carbon tetrachloride was added dropwise to the stirred solution by means of the dropping funnel. Immediately after completion of the dropping were 0.1 wt -.% (Based on the total weight of the content) of tin (II) octoate was added to the solution. The solution obtained in this way was used to carry out the reaction for 146 minutes at 30 ^° C. and 136 minutes

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stirred for a long time at 40 ° C after the addition of 40 ml of distilled Water to improve the stirring efficiency due to the absorption of the solvent by the product after the addition of the catalyst had deteriorated. After the In the reaction, the product was separated into a water-soluble portion and a water-insoluble portion by means of the centrifuge. A solution of the water soluble portion was added to fully stirred acetonitrile to precipitate and a practically colorless, thread-like polymer was obtained. From the infrared absorption spectra, the nuclear magnetic resonance spectra and the titrated value of the base equivalent, it was found that the water-soluble polymer thereby obtained is a carboxylate polyurea with a composition given by y = 0 and χ = 0.744. The portion insoluble in water had one Composition given by y = 0 and zi ^ x.

The measured values with respect to the yield, the softening point and the intrinsic viscosity of the water-soluble polymer were 60.6%, 220.0 to 225.0 ° C and 0.191 ('»)? ° _h ^C / m-cresol) .

A 0.344 mm thick film was prepared from this polymer in the same manner as in Example 3. When measuring under the same conditions as in Example 3 was the specific

12 Volume resistance of the film 1.6 10 ohm cm at 100 V, 8.7 10 ¹¹ ohm cm at 250 V, 4.5 10 ¹¹ ohm cm at 400 V

and 8.6 χ 10 Ohm χ cm at 1000 V, and the specific upper

12 sheet resistance was 4.2 to 2.6 χ 10 ohms for voltages

within the range of 100 to 1000 V / i.e. the electrical Resistance was sufficiently low and devoid of any dielectric

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Fail. Measured in the same way as in Example 3

The amount of charge was 1.64 e.s.Uo / cm.

Example 20

Using the same apparatus as in Example 1, 10.0 g (0.055 mol) of N- (2-carboxyethyl) -p-phenylenediamine (mp 183.0 to 15.5 ° C.) and a solution of 2.21 g Sodium hydroxide (0.0553 mole) in 50 ml of degassed distilled water was added to the flask, purged with nitrogen, and stirred while the flask was held at 22 ° C. A solution of 9.29 g (0.0553 mol) of hexane-1,6-diisocyanate and 50 ml of carbon tetrachloride was added dropwise to the stirred solution using the dropping funnel over a period of 25 minutes. Immediately after completion of the dropping were 0.1 wt -.% (Based on the total weight) of tin (II) octoate was added to the solution to conduct the reaction 155 minutes was stirred at 20 C and 345 minutes at 45 C. After the completion of the reaction, the product, which was in an emulsion state, was added to the fully stirred non-solvent acetonitrile to precipitate, and then separated into a water-soluble portion and a water-insoluble portion. The water-soluble portion was again added to acetonitrile for precipitation, and a dark gray polymer was obtained. From the infrared absorption spectra, the nuclear magnetic resonance spectra and the titrated value for the base equivalent, it was found that the water-soluble polymer thus obtained was a carboxylate polyurea having a composition given by y - 0 and χ = 0.907. The portion that is insoluble in water

809835/0770

had a composition given by y = O and z >> x

The measured were related to the yield, the softening point and the intrinsic viscosity of the water soluble polymer

was 75.9 %, 228 to 230 ° C or 0.305 ( Ή ? °, ^C / m-cresol). This

/ mn

water-soluble polymers had a chelating ability with Transition metals.

A 0.40 mm thick film was prepared from the polymer in the same manner as in Example 3. When measured under the same conditions as in Example 3, the volume resistivity of the film was 2.8 10 cm at 100 V, 1.2 10 ⁹ cm at 250 V and 9.3 χ 10 ^{7 cm} cm at 500 V, and the specific surface resistance was 3.0 10 ohms at 100 Y, 5.1 χ ΙΟ ⁹ ohms at 250 V and 5.6 10 ⁹ ohms at 500 V - ie sufficiently low electrical resistances were obtained . The amount of charge measured in the same way as in Example 3 was 0.44 esu / cm - a very low value. The dielectric properties of the water-soluble polymer (of Example 20) were determined. The measurement was made

at 20 C with compression deformation of the powdery polymer

2
carried out under a pressure of 100 kg / cm. As a result, the following low dielectric constants were obtained, although a polar residue was contained therein.

Hz 60 3 ε ¹ tan δ 231 0 ε " , 000 2 .76 0 108 0 .870 1 , 000 2 .94 0 0697 0 .317 10 .64 0 .184

809835/0770

Example 21

Using the same apparatus as in Example 1, 8.00 g (0.0194 mol) of N _/ N'-di (2-carboxyethyl) -3 _/ 3 ^{l of} dichloro-4,4'-diaminodiphenylmethane (F. 163, 0 to 165.0 C) and a solution of 1.56 g (0.039 mol) sodium hydroxide in 50 ml of degassed distilled water were added to the flask, purged with nitrogen and stirred while the flask was kept in the water bath at 25 ° C . A solution of 4.86 g (0.0194 mol) of diphenylmethane - ^^ '- diisocyanate in 50 ml of carbon tetrachloride was added dropwise to the stirred solution by means of the dropping funnel. 30 minutes after the end of the dropwise addition, 0.1% by weight (based on the total weight) of tin (II) octoate was added to the solution, which was continuously stirred at 40 ° C. for a further 920 minutes to carry out the reaction. The product obtained was separated into an aqueous phase, an organic phase and an insoluble fraction. After the insoluble fraction had been filtered off and separated off, the aqueous phase and the organic phase were separated from one another by means of the separating funnel. The aqueous phase was added to the fully stirred nonsolvent acetonitrile for precipitation to give a powdery polymer. From the infrared absorption spectra, the nuclear magnetic resonance spectra and the titrated value for the base equivalent, it was found that the water-soluble polymer thus obtained was a carboxylate polyurea having a composition given by y = 0 and χ = 0.831. The portion insoluble in water had a composition given by yi 0 and "ζ >> χ.

809835/0770

The measured values related to the yield, the softening point and the intrinsic viscosity of the water soluble polymer

were 90.8 %, 195 to 200 ° C and 0.103 (*} . °. ^C / m-cresol).

'inn

When an aqueous solution of this water-soluble polymer was added to an aqueous solution of a transition metal salt, precipitation occurred, indicating that the polymer had chelating ability would have.

Example 22

Using the same apparatus as in Example 1, 3.00 g (0.0159 mol) of N- (2-carboxyethyl) hexamethylenediamine (CEHD) and 0.329 g (0.0137 mol) of lithium hydroxide - this corresponded to that from the measured value of the Acid equivalent of CEHD calculated equivalent - and 40 ml of dimethyl sulfoxide were introduced into the flask, it was stirred until dissolved, it was flushed with nitrogen and kept in a water bath at 18 ° C. 10.9 g of O3, Oo'-diisocyanate propylene glycol (NCO % = 11.3 %), corresponding to the equivalent calculated from the measured value of the base equivalent of CEHD, were dissolved in 10 ml of dimethyl sulfoxide and the resulting solution was poured over using the dropping funnel dripped into the above solution over a period of 45 minutes. After completion of the dropping were 0.1 wt -.% (Based on the total weight) of tin (II) octoate was added to the solution, further to carrying out the reaction 145 minutes at 18 C and was stirred at 80 C for 120 minutes then . An insoluble portion formed in the dimethyl sulfoxide was filtered off and separated, and the filtrate thus obtained was added to the completely stirred non-solution for precipitation.

809835/0770

medium acetone was added and a pale yellowish color was obtained powdered polymer. From the infrared absorption spectra, the nuclear magnetic resonance spectra and the titrated value of the base equivalent, the above polymer was found to be a carboxylate polyurea with one given by y = 0, ζ = 0 and χ = 1 given composition was. The water-insoluble portion had a composition given by y = 0 and z ^> Jib.x.

The measured values of the yield, softening point and intrinsic viscosity of the water-soluble polymer were 60.0 %, 117 to 143 ° C and 0.188 (^ ^ _h ^C / m-cresol) c. When an aqueous solution of this water-soluble polymer Polymer was added to an aqueous solution of a transition metal salt, a precipitate was formed showing the chelating effect.

Example 23

19.4 g of N- (2-carboxyethyl) hexamethylenediamine lithium salt, 400 g of CO, to'-di (aminotricarbamyl) polytetramethylene glycol (amine number 28.1), 19.8 g 4,4'-diaminodiphenylmethane, 11.6 g hexamethylenediamine and 600 g of alumina powder were placed in a 2 liter beaker in an oil bath to achieve melt blending heated to 90 to 100 ° C and then cooled to 60 ° C. To the cooled mixture was 69.7 g of 1-methylbenzene diisocyanate (l-methylbenzene ^^ - diisocyanate / i-methylbenzene ^^ - diisocyanate ratio 80:20) was added and the mixture was again thoroughly stirred and mixed. The resulting mixture was between two parallel, Teflon-coated iron plates poured and for 2 hours at room temperature, then for 2 hours at 80 C and

809835/0770

finally held at 120 ° C. for a further 2 hours. Thereafter the mixture was cooled to room temperature and from deij Form taken out; thus a 1.0 mm thick plate was obtained. When measuring under the same conditions as in Example 3, the amount of electric charge was this

2
Plate only 3 to 4 esu / cm. This molded body thus had satisfactory antistatic properties. The polymer obtained was a carboxylate polyurea with a composition given by χ = 0.25 and y = 0.75.

Example 24

32.1 g of N- (2-carboxyethyl) -p-xylylenediamine lithium salt, 400 g of Cu , Ui'-di (aminotricarbamyl) polytetramethylene glycol (amine number 28.1), 6.8 g of p-xylylenediamine, 1.20 g Water (as blowing agent and component z) and 37.5 g of barium sulfate powder were placed in a 2 liter beaker, heated in an oil bath to 110 to 120 ° C to obtain a homogeneous molten mixture, and then the mixture was cooled to 55 ° C . 6.00 g of silicone oil as foam stabilizer, 0.30 g of tin (II) octoate and 1.50 g of triethylenediamine were added to the cooled mixture, and the mixture was stirred and mixed. To the mixture was further added 61.6 g of hexane-1,6-diisocyanate, and stirred and mixed thoroughly. The mixture thus obtained was injected into a 2 liter paper cup, polymerized for 2 hours at room temperature and then for 3 hours at 100 ° C. to obtain a molded article. The measurement of the carboxylate equivalent by titration and the nitrogen content by elemental analysis showed that this shaped body is a carboxylate polyurea with a = 0.481,

809835/0770

y = 0.493a and ζ = 0.026 given composition.

The molded body became a cube with dimensions of 5.0 cm χ Cut out 2 inches by 2 inches and it became its electric Amount of charge determined under the same conditions as in Example 3, a voltage of 10 KV being applied to the cube became. While the amount of charge was 1.8 e.s.u./cm immediately after charging, it increased to about 5 to about 1/20 des When the measurement was made after leaving the cube in the same atmosphere for 15 minutes and exposed to natural discharge, indicating satisfactory antistatic properties.

Example 25

4.00 g (0.0206 mol) of N- (2-carboxyethyl) hexamethylenediamine lithium salt, 2.5 g of lithium chloride as an electrolyte solubilizer and 110 ml of dimethyl sulfoxide (DMSO) were introduced together into the same flask as in Example 1, with nitrogen purged and stirred to dissolve at 7O ⁰ C. A solution of 3.46 g (0.0206 mol) of hexamethylene diisocyanate in 20 ml of DMSO was then added dropwise to the stirred solution using the dropping funnel over a period of 15 minutes, the flask being kept at 20 ^° C. After completion of the dropping, 0.28 g of dibutyltin dilaurate solution were added and this was used to conduct the reaction for 120 minutes at 22 ° C and then for 170 minutes at 7O ⁰ C gerührt..Das product from which the major part insoluble in DMSO was filtered off and separated. This insoluble portion was dissolved in water and the resulting solution became soluble in water

809835/0770

Fraction and separated into a fraction insoluble in water. The filtrate was added to acetonitrile to precipitate and a pale yellow powdery polymer was obtained.

The measured values for the yield and the intrinsic viscosity of this water-soluble polymer were 58.3 % and 58.3%, respectively.

30 ° C
0.158 (^ j., / M-cresol), the polymer exhibiting very high moisture absorption properties. From the nuclear magnetic resonance spectrum, it was found that this polymer was a carboxylate polyurea composed of only the x unit.

Example 26

Using the same apparatus as in Example 1, 4.93 g (0.0265 mol) of N- (2-carboxyethyl) -p-phenylenediamine-Ii thium salt, 2.0 g of lithium chloride as an electrolyte solubilizer and 80 ml of dimethyl sulfoxide (DMSO ) jointly introduced into the flask, flushed with nitrogen and stirred to dissolve at 4O ⁰ C. A solution of 6.62 g (0.0265 mol) of 4,4'-diphenylmethane diisocyanate in 20 ml of DMSO was then added dropwise to the stirred solution using the dropping funnel over a period of 13 minutes, the flask being kept at 22 ° C. After the completion of the dropping, 0.22 g of dibutyltin dilaurate was added to the solution, which was stirred at 20 ° C. for 110 minutes and then at 71 ° C. for 125 minutes to conduct the reaction. An insoluble portion of the product was filtered off and separated, and the resulting filtrate was added to acetonitrile for precipitation to obtain a black powdery polymer.

809835/0770

The measured values relating to the yield, the softening point and the intrinsic viscosity of this polymer were 80.1 % _f 230 to 237 ° C. and 0.152 (V ? °, / DMSO), respectively. The nuclear magnetic resonance spectrum of this polymer showed that it was a carboxylate polyurea which consisted only of the x inlet.

Example 27

Using the same device as in Example 1 were 4.00 g (θ, 0206 mol) of N- (2-carboxyethyl) hexamethylenediamine lithium salt, 2.5 grams of lithium chloride as an electrolyte solubilizer and 110 ml of dimethyl sulfoxide (DMSO) together in the flask introduced, flushed with nitrogen and stirred at 70 ° C. to dissolve. Thereafter, a solution of 5.15 g (0.0206 mol) of 4,4'-diphenylmethane diisocyanate was obtained in 20 ml of DMSO added dropwise to the stirred solution using the dropping funnel over a period of 35 minutes keeping the flask at 25 ° C. Islach termination After the dropping, 0.28 g of dibutyltin dilaurate was added to the solution, then it was allowed to conduct the reaction for 110 minutes Stirred for a long time at 26 ° C. and for 120 minutes at 71 ° C. An insoluble one Portion of the product was filtered off and the filtrate obtained was added to acetonitrile for precipitation, whereby a practically ^ colorless powdery polymer obtained.

The values measured in relation to the softening point yields the intrinsic viscosity of this water-soluble polymer} £ 2.9 fS, .207 to ^ 18 ° C or 0.229 {η . , / DT-TSO). From the

this polymex was found

it was a carboxylate polyurea that only consisted of the x-unit *

Example 28

Using the same apparatus as in Example 1, 4.00 g (0.020ό mol) of N- (2-carboxyethyl) hexamethylenediamine lithium salt, 1.24 g (0 _r G207 mol) of ethylenediamine, 2.0 g of lithium chloride were used as Electrolyte solubilizer and 100 ml dimethyl sulfoxide (DMSO) introduced together into the flask, purged with nitrogen and stirred at 70 ° C. to dissolve. A solution of 10.32 g (0.0413 mol) of 4,4 * -diphenylmethane diisocyanate in 20 ml of DMSO was then added dropwise to the stirred solution using the dropping funnel, the flask being kept at 30.degree. After completion of the dropping, 0.27 g of dibutyltin dilaurate was added to the solution, which was stirred at 30 ° C. for 200 minutes and then at 70 ° C. for 120 minutes to conduct the reaction. The product, which was a colorless, transparent, highly viscous liquid, was added to acetonitrile for precipitation, thereby obtaining a colorless, fibrous polymer.

The measured values with respect to the yield, the softening point and the intrinsic viscosity of this polymer were 100 %, 210 to 223 ° C. and 0.364 ° / DMSO). The nuclear magnetic resonance spectra of this polymer showed that it was a carboxylate polyurea which consisted of x and y units.

Claims (1)

DIPL.ING. DIETRICH LEWALD PATENT ADVOCATE D-80C0 MUNICH IO BlBNAJEB. SlRASSE β TELEPHONE 30 05 14 (+ 3 «0 70 8Ϊ) " IN O. nxBTllICIX LbWALD - 8 MÜNCIIRN 4U HlRMAtTKU STR. ft 52 P 756-2 Applicant: NHK-SPEING CO., HED *, 1 Shinisogo-cho, Isogo-ku _? Tokohama-shi, Japan Urea compound with a carboxylate residue and Process for their manufacture Patent claims 1. 'Urea compound with a carboxylate residue, marked by the general formula ox X ¹ O ox X ¹ O χ x'o. R ₀ -COO M ^{+ R} 5 ^R 6 where mean: Rxj is a divalent hydrocarbon radical having 2 to 4 carbon atoms or a divalent polymer radical having an average molecular weight of 10,000 or less,
Ri Riii R2 denotes the -O ^ - 0 ° ·· radical, with the d.-carbon atom Rii Riv
directly to the carbon atom of the carboxylate residue is bound, Ri, Rii, Riii and Riv independently 809835/0770 ! NSPECTED from each other in each case a hydrogen atom, a monovalent hydrocarbon radical having 1 to 10 carbon atoms or represent another monovalent radical that does not have isocyanato or amino radicals reacts, where at least one of the radicals Ri and Rii represents a hydrogen atom, R, a divalent hydrocarbon radical with 4 to 25 carbon atoms or a polyether or polyester residue with an average molecular weight of 10,000 or less, R ₂ , a divalent hydrocarbon radical with 2 to 17 carbon atoms, Rc and Rg each independently represent a hydrogen atom or a monovalent hydrocarbon radical with 1 to 8 carbon atoms or R, - and Rg divalent hydrocarbon radicals formed by mutual Bond together form a carbon chain with 2 to 13 carbon atoms, or their side enkett ensub stituent en, X and X ¹ independently of one another each represent a hydrogen atom or the -COHH radical, M ⁺ a cation and x, y and ζ values which indicate the relative molar proportions of the respective corresponding units and meet the required conditions: x + y + z = 1 and 0.1 <100x / (x + y + z) <100. 2, urinary off connection according to claim 1, characterized 809835/0770 draws that j and ζ each represent the number O "and that it is represented by the formula OX X ¹ O Μ ι ι Il (-HNR, NCNR ₀ NC -) - J. τ ο Χ R ₂ -COcTm ⁺ wherein R ^, Rp » ^E zi ^x » ^x 'u ¹¹ ^ ^{M + d} ^ ^e ^ claim 1 have given meanings. 3. Urnst of f connection according to claim 1, characterized in that that ζ means the number 0 and that it is represented by the formula OX X ¹ O OX X ¹ O It I Il. Ill I 11 f-HNR, NCNR-jN-C-) (-NR. NCNR-N-C-) 1 | 3 x j 4 | 3 'y R - COO ~ M ⁺ R- R-. wherein R ₁ , R ₂ , R ^, R ^, R ^, R ₆ , X, X ¹ and M ^{+ have} the meanings given in claim 1 and χ and y represent values which indicate the relative molar proportions of the respective corresponding units and meet the required conditions: x + y = 1 and 0.1 <i00x / (x + y) <100. Urea compound according to claim 1, characterized in that that y means the number O and that it is represented by the formula 809835/0770 OX X ¹ OXX ¹ O III I Il Il Il (-HNR ₁ NCNR, NC-} (ΝΚ, Ν-Ο) R ₂ -COcTm ⁺ where ILj, R ₂ ,%> ^x » ^χι ^ ^{110 M + d3} - ^e ^ - ⁿ claim 1 have given meanings and χ and ζ represent values which indicate the relative molar proportions of the respective corresponding units and meet the required conditions: x + z = 1 and 0.1 <100x / (x + z) <100. 5- urea compound according to claim 1, characterized in that that x, y and ζ each represent a number greater than 0 and that it is represented by the formula ox x'o. ox x'o χ x'o , NCNR ^ NC} ^ NRi ₁ NCNR ₀ NCH £ -NR-, N- ( Li 3x. | 4f ό y S I - j. rl R ₀ -COO M LR, Z DO wherein R ₁ , R ₂ , R ^, R ^, Rc, Rg, X, X ¹ and M ^{+ have} the meanings given in claim Λ and x, y and ζ represent values which indicate the relative molar proportions of the respective corresponding units and meet the required conditions: x + y + z = 1 and 0.1 <100x / (x + y + z) <i00. 6. urea compound according to claim 1, characterized 809835/0770 indicates that the molar amount of the -CONH radical is 30 % or less of the total ^{molar amount of the X and X 1} radicals. 7 · Urea compound according to claim 1, characterized in that the radical R ^ is selected from the group of aliphatic hydrocarbon radicals with 2 to 1? Carbon atoms; the alicyclic or aliphatic-substituted alicyclic hydrocarbon radicals having 6 to 1'5 carbon atoms; the aromatic, aliphatic-substituted aromatic and aliphatic-substituted alicyclic-substituted aromatic hydrocarbon radicals; the derivatives thereof substituted by non-hydrocarbon radicals; and the u) _% ω '-PoIyäther- and U , ^' - polyester radicals, each of which has a repeating unit with 2 to 20 carbon atoms and an average molecular weight of 104 to 10,000. 8. urea compound according to claim 7 »characterized in that R / j is an ethylene, hexamethylene, p-phenylene, p-xylylene, 4, M- '-diphenylenemethane or 3,3' -dichloro-4, 4 -'-diphenylenemethane radical means. 9. urinst off connection according to claim 1, characterized in that that the radicals Ri, Rii, Riii and Riv are radicals which are selected from the group of aliphatic, alicyclic and aromatic hydrocarbon radicals each having 1 to 10 carbon atoms; the monovalent hydrocarbon radicals derived from a combination thereof; Halogen atom; Cyano residue; Amide residue; Imide residue; Nitro residue; Ester residue; 8098 3 5/0770 Alkoxy esters; Aryloxy esters; Ketone est; and oxycarbonyl esters. 10. urea compound according to claim. 9 »characterized by that Eq is an ethylene or <x -methylethylene Eest. 11. Urea compound according to claim 1, characterized in that E, denotes an Eest which is selected from the group of aliphatic hydrocarbon Eeste with 4 to 16 carbon atoms, the alicyclic hydrocarbon off Eeste with 8 to 20 carbon atoms, the aliphatic-substituted aromatic hydrocarbon groups with 9 to 20 carbon atoms, the alicyclically substituted aromatic hydrocarbon groups with 12 to 20 carbon atoms, the aromatic hydrocarbon groups with 8 to 25 carbon atoms and the Cü , U) 'polyether and ω , i ^' polyesters -Eests, each having an average molecular weight of 302 to 10,000. 12. Urnst off connection according to claim 11, characterized in that that E, a hexamethylene, diphenylmethane, 1-methyl-2,4-phenylene or 1-methyl-2,6-phenylene radical means. 13. urea compound according to claim 1, characterized in that that M is a member selected from the group consisting of the alkali metals, the alkaline earth metals and the tertiary amines. . Process for the production of a urea compound with 809835/0770 a carboxylate residue represented by, the general formula is pictured ox x'o ox x'o χ X ¹ O im ι ι im r ti ti ι J ₁ HNR ₁ NCNR-NC-) (-NR.NCNR-NC -) - (-NR-NC -) --- ^v l | 3 'χ -ι 4 ι 3 y 3 ζ R ₂ -COO ~ M ⁺ R ₅ Rg in particular such, according to claims 1 to characterized in that an amino amino carbon acid salt of the formula H ₂ NR ₁ HH R ₂ -COO ^- M ⁺ with a diisocyanate of the formula OCNR ₅ NCO, optionally reacted in the presence of water and / or a diamine of the formula HN R ₄ NH Rq Rg where mean: R / j is a divalent hydrocarbon radical with 2 to 17 carbon atoms or a divalent polymer residue with an average molecular weight 809835/0770 of 10,000 or less, Egg egg
E ₀ denotes the Eest -C - C -, in which the oL carbon atom Eii Eiv
is bonded directly to the carbon atom of the carboxylate Eestes, Ei, Eii, Eiii and Eiv each independently a hydrogen atom, a monovalent hydrocarbon Eest with 1 to 10 carbon atoms or another monovalent Eest that does not react with isocyanato or amino Eeste , represent, where at least one of the radicals Ei and Eii is a hydrogen atom, E, a divalent hydrocarbon residue with 4 to 25 carbon atoms or a polyether or polyester Eest with an average molecular weight of 10,000 or less, E ^ a divalent hydrocarbon Eest with 2 to 17 carbon atoms, Ec and Eg each independently represent a hydrogen atom or a monovalent hydrocarbon radical with 1 to 8 carbon atoms or Ε _κ and E ^ divalent hydrocarbon radicals which together form a carbon chain with 2 to 13 carbon atoms through mutual bonding, or they have side chain substituents, X and X ¹ each represent a hydrogen atom or the -COKH-Ee st, M ⁺ a cation and 809835/0770 x, y and ζ values representing the relative molar proportions of the respective corresponding units and meet the required conditions: x + y + z = 1 and o, 1 <ioox / (x + y + z) ^ 100. 15. The method according to claim 14, characterized in that only the aminoaminocarboxylic acid salt and the diisocyanate represent un permissible reactants and that you urinate off compound of the formula οχ χ Ό IM I I (HNR ₁ NCNR-NC-) R ₂ -COO ~ M ⁺ wherein R ₁ , R ₂ , R ,, X, X 'and M ^{+ have} the meanings given in claim 14-. 16. The method according to claim 14, characterized in that the aminoaminocarboxylic acid salt, the diisocyanate and the Biamin represent the essential reactants and that a urea compound of the formula is prepared ox x'o ox x'o «I I Il III I ΪΙ__ (-HNR ₁ NCNR-.NC} - (-NR NCNR.NC -) --- Ii -3 X Il R ₂ -COO MR ₅ Rg wherein R ₁ , R ₂ , R ,, R ^, Rc, Sg, X, X ¹ and M ^{+ have} the in 809835/0770 Claim. 14 have given meanings and χ and y Represent values which indicate the relative molar proportions of the respective corresponding units and the The required conditions are satisfied: x + y = 1 and 0.1 ^ 100x / (x + y) <100. 17 · Method according to claim. 14, characterized in that the aminoaminocarboxylic acid salt, the diisocyanate and the Water represent indispensable reactants and that a urea compound of the formula is prepared OX Χ ^Γ 0 XX ¹ O 111 (B. ^ -HNR ₁ NCNR ₃ NC-; R ₂ -COO M wherein R ₁ , R ^ ₁ R ,, X, X ¹ and M ^{+ have} the meanings given in claim 14 and χ and ζ denote values which indicate the relative molar proportions of the respective corresponding units and meet the required conditions: x + z = 1 and Ο, 1 ^ 1ΟΟχ / (χ + ζ) <.1OO. 18. The method according to claim 14, characterized in that the aminoaminocarboxylic acid salt, the diisocyanate, the diamine and water are all essential reactants and that one is a urea compound of the formula manufactures OX X ¹ O OX X ¹ OXX ¹ O -4HNR ₁ NCNR ^ N-CJ ^ - (NR ₄ NCNR ₃ N-CTy R "-C00 M" Rc- R, - 2 3D 809835/0770 where ILp E ₂ *% »%» ^E 5> ^E 6 » ^x » ^x '^ ^{110 M + die} Spruch 14- have given meanings and x, y and ζ Values which indicate the relative molar proportions of the respective corresponding units and the meet the required conditions: x + y + z = 1 and 0.1 <i00x / (x + y + z) <i00. 19. The method according to claim 14, characterized in that the reaction is an interfacial polyaddition reaction acts. 20. The method according to claim 19, characterized in that water is used as a solvent for the aminoaminocarboxylic acid salt and that as a solvent for the diisocyanate a water-insoluble organic solvent is used which is mixed with the aminoaminocarboxylic acid salt and the diisocyanate does not react. 21. The method according to claim 20, characterized in that the organic solvent or carbon tetrachloride Methylene chloride is used. 22. The method according to claim 19, characterized in that the aminoaminocarboxylic acid salt is prepared by adding the base M to the corresponding aminoaminocarboxylic acid before the reaction. 23. The method according to claim 19, characterized in that the reaction is carried out using a first Stage in which the reaction takes place at a relatively low temperature and in the absence of a catalyst is carried out, a second stage in which the 809835/0770 Reaction carried out in the presence of a catalyst
a third stage in which the reaction is carried out at a relatively high temperature, or a combination thereof. 24. The method according to claim 20, characterized in that the concentration of each of the reactants in each of the solvents Is 0.1 to 40% by weight. 25. The method according to claim 20, characterized in that the concentration of each of the reactants in each of the solvents is 1 to 30% by weight. 26. The method according to claim 20, characterized in that the reaction at a temperature above the freezing point of the reaction system to less than 100 ⁰ C.
is carried out. 27. The method according to claim 26, characterized in that the reaction is carried out at a temperature below the boiling point of the organic solvent
will. 28. The method according to claim 20, characterized in that 'the reaction at a temperature of 0 to 60 ⁰ C is carried out. 29. The method according to claim 20, characterized in that the reaction is carried out at a temperature of 0 to 35 ^0C . 30. The method according to claim 23, characterized in that 809835/0770 the reaction is carried out in the way _? that the first stage is carried out until the majority of the reaction has been completed and that the third stage is then carried out at a temperature which is from 5 to 35 ° C. higher than the temperature at which the first stage has been carried out to the Reaction to complete eventually. 31 · The method according to claim 14, characterized in that the reaction is a solution polymerization. 32. The method according to claim 31 »characterized in that a polar aprotic solvent is used. 33. The method according to claim 32, characterized in that an electrolyte is added as a solubilizing agent, which does not react with the diisocyanate, the aminoaminocarboxylic acid salt and the polar aprotic solvent. 34. The method according to claim 32, characterized in that the corresponding aminoaminocarboxylic acid and the base M are added to the polar aprotic solvent for neutralization is added to form a solution of the aminoaminocarboxylic acid salt. 35 * The method according to claim 34, characterized in that a neutral dehydrating agent is added to remove the water formed during neutralization. 36. The method according to claim 32, characterized in that 809835/0770 a solution of the diisocyanate is slowly added to a solution of the aminoaminocarboxylic acid salt. 37 · The method according to claim 32, characterized in that the reaction is carried out in an inert atmosphere. 38. The method according to claim 31 »characterized in that the reaction is carried out at a temperature above the freezing point of the reaction system up to 200 ° C. 39. The method of claim 31 'characterized in that up to 100 ⁰ C the reaction is performed at a temperature above the freezing point of the reaction system. 40. The method according to claim 31 »characterized in that the reaction is carried out using a first stage in which the reaction is carried out at a relatively low level Temperature and in the absence of a catalyst is carried out, a second stage in which the reaction is carried out in the presence of a catalyst, a third stage in which the reaction at a relatively high temperature, or a combination thereof. 41. The method according to claim 40, characterized in that the reaction is carried out by the first stage until the completion of most of the reaction carried out and that you then the third stage at a Performs temperature that is 5 to 100 ° C higher than 809835/0770 the temperature at which the first stage was carried out to ultimately complete the reaction. 42. The method of claim 31, characterized in that the concentration of each of the reactants in each of the solvents 1 to 50% by weight. 43. The method according to claim 31 »characterized in that the concentration of each of the reactants in each of the solvents 5 to 30% by weight. 44. The method according to claim 14, characterized in that the reaction is a solvent-free one
Polymerization acts. 45. The method according to claim 40, characterized in that the reactants are mixed together in a container
or introduced into a mold and together
implemented. 46. The method according to claim 44, characterized in that the reaction is carried out using a first Stage in which the reaction takes place at a relatively low temperature and in the absence of a catalyst is carried out, a second stage in which the reaction is carried out in the presence of a catalyst, or a combination thereof. 47. The method according to claim 46, characterized in that the first stage at a temperature of 0 to 100 ⁰ C
is carried out. 809835/0770 48. A method according to claim 46, characterized in that the reaction is carried out and that the second stage at a temperature of 50 to 200 ⁰ C is carried out using a combination of the first stage and from the second stage. 49. The method according to claim 44, characterized in that a diluting filler is added. 50. The method according to claim 49, characterized in that aluminum oxide powder or barium sulfate powder is used as the diluting filler is used. 80983 5/0770